biostudies-literatureLaurent QSwiss National Science FoundationNational Centre of Competence in Research (NCCR), Chemical BiologyNational Centre of Competence in Research (NCCR), Molecular Systems EngineeringUniversité de Genèvee202200785https://www.ebi.ac.uk/biostudies/studies/S-EPMC9324982biostudies-literatureUnknown28(33)A model system is introduced as a general tool to elaborate on orthogonal templation of dynamic covalent ring-opening polymerization (ODC-TROP). The tool consists of 3₁₀ helical peptides as unprecedented templates and semicarbazones as orthogonal dynamic covalent linkers. With difficult-to-control 1,2-dithiolanes, ODC-TROP on the level of short model oligomers occurs with high templation efficiency, increasing and diminishing upon helix stabilization and denaturation, respectively. Further, an anti-templated conjugate with mispositioned monomers gave reduced templation upon helix twisting. Even with the "unpolymerizable" 1,2-diselenolanes, initial studies already afford mild templation efficiency. These proof-of-principle results promise that the here introduced tool, recyclable and enabling late-stage side chain modification, will be useful to realize ODC-TROP of intractable or unknown cyclic dynamic covalent monomers for dynamer materials as well as cellular uptake and signaling applications.Chemistry (Weinheim an der Bergstrasse, Germany)An Orthogonal Dynamic Covalent Chemistry Tool for Ring-Opening Polymerization of Cyclic Oligochalcogenides on Detachable Helical Peptide Templates.PMC9324982200020_204175Matile SLaurent QSakai NfalseAn Orthogonal Dynamic Covalent Chemistry Tool for Ring-Opening Polymerization of Cyclic Oligochalcogenides on Detachable Helical Peptide Templates.A model system is introduced as a general tool to elaborate on orthogonal templation of dynamic covalent ring-opening polymerization (ODC-TROP). The tool consists of 3₁₀ helical peptides as unprecedented templates and semicarbazones as orthogonal dynamic covalent linkers. With difficult-to-control 1,2-dithiolanes, ODC-TROP on the level of short model oligomers occurs with high templation efficiency, increasing and diminishing upon helix stabilization and denaturation, respectively. Further, an anti-templated conjugate with mispositioned monomers gave reduced templation upon helix twisting. Even with the "unpolymerizable" 1,2-diselenolanes, initial studies already afford mild templation efficiency. These proof-of-principle results promise that the here introduced tool, recyclable and enabling late-stage side chain modification, will be useful to realize ODC-TROP of intractable or unknown cyclic dynamic covalent monomers for dynamer materials as well as cellular uptake and signaling applications.2022-01-01T00:00:00Z2022 Jun2025-04-26T16:13:32.845Z2025-04-06T15:10:28.772ZS-EPMC93249823541634510.1002/chem.202200785